Permanent wave agent composition having dyeing effect and method for dyeing hair using the same

ABSTRACT

A second agent composition for permanent wave treatment having a dyeing effect and a method for dyeing the hair which has been permanently waved. More particularly, a second agent composition for permanent wave treatment comprising a cationic dye having a quaternary nitrogen atom, which is optionally delocalizable, and a —X═N— bond wherein X represents a nitrogen atom or a —CH— bond, and a method for dyeing the hair which has been subjected to a permanent wave treatment using the cationic dye.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a national stage application under 35 U.S.C. § 371of international application PCT/JP99/000523 filed on Feb. 8, 1999, theinternational application not being published in English. Thisapplication also claims priority under 35 U.S.C. 119 to JP 28797/1998,filed on Feb. 10, 1998.

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a solution composition of a permanentwaving composition having a hair dyeing effect and a method for dyeinghair using the same.

BACKGROUND OF THE INVENTION

In general, a permanent waving composition comprises a first solution(reducing agent) containing thioglycolic acid and the like as a mainingredient, and a second solution (oxidative fixing agent) containinghydrogen peroxide, potassium bromate, sodium bromate and the like as amain ingredient, but, hitherto, there has not been found any permanentwaving composition to which a hair dyeing effect is imparted.

Under these circumstances, a first object of the present invention is toprovide a permanent waving composition to which a hair dyeing effect isimparted and which is excellent in stability, dyeability and fastness.

A second object of the present invention is to provide a method fordyeing hair comprising dyeing the hair, which has been permanentlywaved, with the composition as described above.

DISCLOSURE OF THE INVENTION

In order to obtain a permanent waving composition to which a hair dyeingeffect is imparted, the present inventors added to a second solution ofa permanent waving composition various dyes including an acidic dye anda tar-series pigment which has been conventionally used in general as adye for a hair dye, and studied their stability, dyeability and fastnessto light or to hydrolysis (hereinafter, simply referred to as“fastness”). As the result, it was found that certain cationic dyeswhich are proposed to be a suitable dye for a hair dye in recent years(EP 714954A, WO 95/01772 and WO 95/15144 (JP-A 8-507545)) have the mostexcellent stability, dyeability and fastness. Also, it was found that,when said cationic dye is used to dye hair, which has been permanentlywaved, the hair can be dyed with high dyeability, without deterioratingthe effect of permanent waving.

That is, the present invention was completed based on such theinventor's novel findings and, in the first embodiment thereof, there isprovided a second solution composition of a permanent waving compositioncomprising a cationic dye having a quaternary nitrogen atom which mayoptionally be delocalizable and a —X═N— bond, wherein X means a nitrogenatom or —CH—.

According to the first embodiment of the present invention, a secondsolution of a permanent waving composition having high dyeing anddyeing-fastness effect can be provided.

Moreover, in the second embodiment, the present invention provides amethod for dyeing hair comprising dyeing hair, which has beenpermanently waved, with a composition comprising a cationic dye having aquaternary nitrogen atom which may optionally be delocalizable and a—X═N— bond, wherein X means a nitrogen atom or —CH—.

According to the second embodiment of the present invention, there isprovided a method for dyeing hair which exerts high dyeing effect anddyeing-fastness, without deteriorating the effect of permanent waving.

The present invention will be illustrated below in more detail by way ofthe first and second embodiments in this order.

[First Embodiment]

The second solution of the permanent waving composition according to thefirst embodiment of the present invention is one in which the cationicdye as described above is incorporated into or combined with aconventional second solution of the permanent waving composition.

As the cationic dye to be used in the first embodiment of the presentinvention, there is a cationic dye represented by the formula (I):[A—Z═N—B]⁺X⁻  (I)wherein Z means a nitrogen atom or —CH—; A and B mean an aromaticbenzene ring or heterocycle which may be optionally substituted with oneor more of halogen atoms or one or more of NR₁R₂ or OR₁ groups; whereinR₁ and R₂ are the same or different and independently mean hydrogen,C₁₋₈ alkyl, C₁₋₄ hydroxyalkyl or phenyl; and X⁻ means an anion. Thiscationic dye is described in detail in the above-described EP 714954A,WO 95/01772 and WO 95/15144 (JP-A 8-507545).

As a preferred anion, there are chloride, methylsulfate and the like.

Representative examples of the cationic dye are:4-aminophenylazo-2-hydroxy-7-trimethyl ammoniumnaphthalene chloriderepresented by the formula (1):

2-methoxyphenylazo-2-hydroxy-7-trimethylammoniumnaphthalene chloriderepresented by the formula (2):

4-amino-3-nitrophenylazo-2-hydroxy-7-trimethylammoniumnaphthalenechloride represented by the formula (3):

3-trimethylammoniumphenylazo-4N-phenyl-2-methyl-5-hydroxypyrazolechloride represented by the formula (4):

(1-methyl-1-phenyl)₂-(1-methine-4N-methylpyridinium)hydrazine chloriderepresented by the formula (5):

(1-methyl-1-paramethoxyphenyl)2-(1-methine-methylpyridinium)hydrazinechloride represented by the formula (6)

(1-methyl-1-paramethoxyphenyl)-2(1-methine-4N-methylpyridinium)hydrazinemethyl sulfate represented by the formula (7):

4-dimethylaminophenylazo-2N-methyl-S5-methylimidazolium chloriderepresented by the formula (8)

4-dimethylaminophenylazo-2N-methyl-5N-methylpyrazolium chloriderepresented by the formula (9):

4-dimethylaminophenylazo-2N-methyl-5N-methylimidazolium chloriderepresented by the, formula (10):

4-aminophenylazo-2N-methyl-5N-methylimidazolium chloride represented bythe formula (11):

4-dimethylaminophenylazo-4N-methylpyridinium chloride represented by theformula (12):

and 4-dimethylaminophenylazo-4N-oxidopyridinium chloride represented bythe formula (13):

The above cationic dyes may be used alone or in a combination with twoor more thereof, and an amount thereof may be optionally selecteddepending on the desired color but, usually, it is contained at 0.001-3%by weight based on the total amount of the second solution.

The second solution of the permanent waving composition according to thefirst embodiment of the present invention may be formulated into anordinary form according to such the conventional method as mixing thedesired ingredients, and the cationic dye as described above and anoxidizing agent as an essential ingredient of the second solution suchas hydrogen peroxide, potassium bromate, sodium bromate, sodiumperborate and the mixture thereof may be contained therein.Additionally, known ingredients which are usually used such as suitablesolubilizing agents, permeating agents, lubricants, hair restorers,emulsifying agents, and perfumes may be optionally contained in thesecond solution. Alternatively, the dye and the oxidative fixingsolution may be prepared into separate compositions to form atwo-packages composition and the separate compositions may be mixed uponapplication.

The second solution of the permanent waving composition according to thefirst embodiment of the present invention may be used in the same manneras that of the known second solution and, in the case of thetwo-packages composition, the separate compositions may be mixed uponapplication.

[The second Embodiment]

The method for dyeing hair according to the second embodiment of thepresent invention can be conducted by dyeing the hair, which has beenpermanently waved, with the composition as described above.

In the case of the two-packages composition, as a dye composition to beused, an aqueous solution containing 0.001-3% by weight of a cationicdye is preferable. Particularly, an aqueous solution containing waterpreferably at an amount of not less than 60% by weight, more preferablynot less than 80% by weight, which is adjusted to not less than pH 5,preferably pH 5-10 is preferable. For example, the hair dyeing may beconducted by permanently waving the hair with the first solution and thesecond solution not containing the dye, applying the compositioncontaining the cationic dye to the hair, allowing the hair to stand fora suitable time, for example, for 2-30 minutes, adequately washing anddrying. Thus, the hair can be dyed with high dyeability and fastness,without deteriorating the effect of permanent waving.

BEST MODE FOR CARRYING OUT THE INVENTION

Although the present invention will be illustrated in more detail by wayof Test Examples and Examples, the present invention is not intended tobe limited to them. Furthermore, hereinafter, “%” means “% by weight”unless otherwise indicated.

TEST EXAMPLE 1

Stability of a Second Solution of a Permanent Waving CompositionContaining a Direct Dye with Time

Each of an acidic dye, tar-series pigment and cationic dye which are adirect dye was weighed out so as to be 0.2% by weight in terms of theactive ingredient, and added to a second solution of a permanent wavingcomposition formulated as shown in Table 1 to stir.

As the acidic dye. BLACK 401, PURPLE 401 and ORANGE 205 were used. Inthe tar-series pigment, HC BLUE 2 and HC YELLOW 2 (manufactured by JAMSROBINSON Inc.) were used. And, as the catatonic dye, (A):(1-methyl-1-paramethoxyphenyl)-2-(1-methane-4N-methylpyridinium)hydrazinechloride, (B): 4-dimethylaminophenylazo-2N— methyl-5N-methylimidazoliumchloride and (C): 4-aminophenylazo-2N-methyl-5N-methylimidazo iumchloride (manufactured by Ciba Specialty Chemicals, Inc.) were used.

TABLE 1 Ingredient Amount (%) Sodium bromate 8.50 Trisodium phosphate0.27 Phosphoric acid 0.09 Purified water Balance

After stirring for approximately 10 minutes at room temperature, thesecond solution of the permanent waving composition containing the dyewas filtered through a filter (TOYO ADVANTEC No. 2, circle size: 125 mm)to prepare a sample. The sample was stored at 45° C., and stability ofthe sample with time was evaluated for solubility of the dye in thesample, pH, absorption spectra in a visible light range.

The evaluation for solubility of the dye was conducted based on thefollowing criteria:

-   -   ◯: No change in solubility compared to that measured two weeks        before; and    -   X: Precipitation of the dye

A pH was measured with a pH meter manufactured by HORIBA Inc. Limited.Moreover, the evaluation for the absorption spectra in the visible lightrange was conducted by measuring an absorbance at the maximum absorbancewavelength in the absorption spectra in the visible light range usingHITACHI U-3210 (using a quartz cuvette having 10 mm optical path) andcalculating a ratio of the dye that remains solubilized after 4 weeks bydefining the initial measured solubilized value as 100%.

The results are shown in Table 2.

TABLE 2 BLACK PURPLE ORANGE HC HC Cationic Dyes 401 401 205 BLUE 2YELLOW 2 (A) (B) (C) Solubility of dye (45° C.) 2 weeks X X X ◯ ◯ ◯ ◯ ◯4 weeks ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ pH (45° C.) Initial 6.43 6.54 6.44 6.43 6.436.43 6.42 6.41 2 weeks 6.44 6.52 6.43 6.44 6.42 6.42 6.41 6.40 4 weeks6.45 6.54 6.45 6.15 6.44 6.42 6.43 6.41 Ratio of dye that remains 87.092.2 98.7 0.00 97.6 99.6 102.0 solubilized after 4 weeks 98.0 at 45° C.

As shown in Table 2, it was found that the dye which is stable with timein the second solution of the permanent waving composition containingthe dye is the cationic dyes and the tar-series pigment HC YELLOW 2.

TEST EXAMPLE 2

Dyeability and Fastness Tests of a Second Solution of a Permanent WavingComposition Containing a Dye

To approximately 2 g of goat hair, approximately 2 g of a first solutionof a permanent waving composition was applied, and the hair was allowedto stand in a constant temperature bath at 30° C. for 15 minutes. Then,approximately 2 g of the same filtered second solution of a permanentwaving composition as that described in Test Example 1 was applied tothe hair, and the hair was shampooed and treated with a hair rinseconditioner, and adequately rinsed with water. After drying the hair,dyeability for the hair was evaluated.

Thereafter, the hair which was dyed in the dyeability test was allowedto stand for 24 hours after dyeing, then immersed into 300 ml of anaqueous solution containing 0.03/sodium polyoxyethylene (2 E.O.) alkyl(12, 13) ether sulfate at 80° C. for 10 minutes. Then, the hair wasadequately rinsed with warm water, dried, and fastness was evaluated byobserving dyeability for the hair after the test. The evaluation wasconducted based on the following criteria:

-   -   ⊚: Deeply dyed and an original white color of the goat hair is        not prominent    -   ◯: Dyed to a degree that an original white color of the goat        hair is not prominent    -   Δ: Dyed, but prominent in an original white color of the goat        hair    -   X: Only an original white color of the goat hair.

The results are shown in Table 3.

TABLE 3 Dye Dyeability Fastness BLACK 401 ◯ X PURPLE 401 X X ORANGE 205Δ X HC BLUE 2 ◯ X HC YELLOW 2 ◯ X Cationic dyes (A) ⊚ ⊚ (B) ⊚ ⊚ (C) ⊚ ⊚

As shown in Table 3, the cationic dyes show excellent dyeability andfastness.

TEST EXAMPLE 3

Measurement of the Wave Index and Wave Retention Ratio of Hair Which isDyed with a Second Solution of a Permanent Waving Composition Containinga Cationic Dye, and of Hair, which has Been Permanently Waved and,Thereafter, Dyed with an Aqueous Solution of a Cationic Dye

The wave index was evaluated using human hair according to a Kirbymethod.

In the case of dyeing with a second solution of a permanent wavingcomposition containing a cationic dye, the hair was immersed into each50 g of a first solution and a second solution in this order to treat ata treatment temperature of 30° C. for a treatment period of 15 minutes.In this test, the second solution of the permanent waving compositioncontaining 0.05% cationic dye (B) as described above was used and, aftertreating with the second solution, the hair was washed with water andremoved from an implement, and the wave index was measured.

In the case of dyeing the hair which has permanently waved, the hair waspermanently waved with the first solution and the second solution notcontaining the dye according to the same manner as that described above,and after treating with the second solution, the hair was adequatelywashed with water and immersed into a 0.05% aqueous solution of thecationic dye (B) which had been adjusted to pH 9. After treated at atreatment temperature of 30° C. for a treatment period of 30 minutes.The hair was adequately washed with water, removed from the implementand the wave index was measured.

For the wave retention rate, the hair after measuring the wave index wasimmersed into a 20% aqueous solution of sodium laurylsulfate at 60° C.for 20 minutes to perform a severe test, the wave index was measuredaccording to the same manner as that described above, and a ratio of thewave index of the hair after the sever test to that before the severetest was calculated and compared.

As a control, the severe test was performed on the hair treated with thefirst solution and the second solution not containing the dye accordingto the same manner, and the wave indexes before and after the test weremeasured and a wave retention rate of the hair was calculated.

The results are shown in Table 4

TABLE 4 Hair dyed with a Hair dyed with an Hair treated second solutionaqueous solution of with only containing a a cationic dye afterpermanent cationic dye permanent waving waving Wave index (%) 75.3274.81 74.34 Wave retention 74.79 68.39 73.16 rate (%)

As shown in Table 4, the cationic dye does not deteriorate the effect ofpermanent waving.

TEST EXAMPLE 4

Dyeability of a Second Solution of a Permanent Waving CompositionContaining a Cationic Dye and of a Cationic Dye Solution for thePermanently Waved Hair

To approximately 2 g of goat hair, each 2 g of a first solution and asecond solution containing 0.05% of a cationic dye (B) was applied inthis order, and the hair was allowed to stand in a constant temperaturebath at 30° C. for 15 minutes. After the treatment with the secondsolution, the hair was shampooed, treated with a hair rinse conditioner,adequately rinsed with water and dried, and dyeability was evaluated.

Thereafter, each 2 g of the first solution and the second solution notcontaining the dye was applied to the permanently waved hair under thesame condition as that described above. After the treatment with thesecond solution, the hair was adequately washed with water, and 2 g of a0.05/aqueous solution of the cationic dye (B) which had been adjusted topH 9 was applied to the hair which had been permanently waved and theuntreated hair, respectively, which were allowed to stand at a treatmenttemperature of 30° C. for a treatment period of 30 minutes. Then, thehair was shampooed and treated with a hair rinse conditioner, adequatelyrinsed with water and dried, and dyeability was evaluated. Dyeabilitywas evaluated according to a brightness of JIS standard color chart. Thesmaller value thereof indicates higher dyeability.

The results are shown in Table 5.

TABLE 5 Hair dyed with an Hair dyed with a aqueous solution of Untreatedhair second solution a cationic dye dyed with an Dyeing containing aafter permanent aqueous solution of condition cationic dye waving acationic dye Dyeability 4 3.5 5

As shown in Table 5, dyeability is enhanced by permanent waving.

TEST EXAMPLE 5

Effect of a pH of a Cationic Dye on Dyeability

A 0.05% aqueous solution of a cationic dye (C) was adjusted to pH 3, 5,7, 9 or 11, and 4 g thereof was applied to approximately 2 g of goathair. The, hair was allowed to stand in a constant temperature bath at30° C. for 30 minutes. Then, the hair was shampooed and treated with ahair rinse conditioner, adequately washed with water and dried, anddyeability was evaluated according to the same manner as that describedin Test Example 4.

The results are shown in Table 6.

TABLE 6 pH 3 5 7 9 11 Dyeability 6.5 6.0 5.7 5.3 5.0

As shown in Table 6, as a pH of the aqueous solution of the cationic dyegrows higher, dyeability is enhanced. But, since a solution having a pHof not less than 10 is strongly irritative to the human body and,therefore, not suitable for use, the solution may be preferably adjustedto a pH of not less than 5 and more preferably to a pH of 9. Since, ingeneral, a second solution of a permanent waving composition is adjustedto pH 4-10.5 and, more frequently to pH 6-8, it can be expected that thesecond solution of the permanent waving composition exerts highdyeability even when a cationic dye is added to the permanent wavingcomposition. Furthermore, untreated goat hair was dyed in this test, butit is predicted that the hair which has been permanently waved shows asimilar tendency of dyeability depending on the pH to that of theuntreated hair, though rs it merely shows a higher degree of dyeabilitythan that of the untreated hair.

TEST EXAMPLE 6

Effect of Water Content in an Aqueous Dye Solution on Dyeability of aCationic Dye

0.05% aqueous solutions of a cationic dye (C), each containing 0, 10,20, 30, 40 and 50% propylene glycol respectively, were adjusted to pH9.4 g of each solution was applied to approximately 2 g of goat hair,and the goat hair was allowed to stand in a constant temperature bath at30° C. for 30 minutes. Then, the hair was shampooed and treated with ahair rinse conditioner, and adequately washed with water and dyeabilitywas evaluated according to the same manner as that described in TestExample 4.

The results are shown in Table 7.

TABLE 7 Propylene glycol wt % 0 10 20 30 40 50 Dyeability 6.5 6.8 7.07.7 8.5 9.0

As shown in Table 7, since dyeability is considerably lowered byinclusion of propylene glycol of not less than 30%, particularly of 40and 50% in the solution, the water content is preferably not less than70%, more preferably not less than 80%.

EXAMPLE 1

A Second Solution Composition of a Permanent Waving CompositionUtilizing Hydrogen Peroxide

A second solution composition of the following formulation was preparedaccording to the conventional method.

Ingredient % (1-methyl-1-phenyl)-2-(1-methine-4N-methylpyridinium) 0.2hydrazine methylsulfate Hydrogen peroxide (35%) 4.3 Cetanol 0.5 Reducedlanolin 0.35 Acetanilide 0.02 Sodium pyrophosphate 0.025 Phosphoticacid, purified water Balance (A pH was adjusted to 6.5 with phosphoricacid)

The formulation of a first solution used was as follows.

Ingredient % Ammonium thioglycolate solution 13.6 (50% as thioglycolicacid) Ammonium bicarbonate 3.5 Disodium editate 0.1 Monoethanolamine,purified water Balance (A pH was adjusted to 9.0 with monoethanolamine)

The permanent waving and dyeing treatment of the hair were performed asfollows. According to the conventional method, a tip of the white hairwas protected with paper, then the hair was wound to a plastic rodhaving a 1.5 cm diameter, immersed into the first solution as describedabove at 30° C. for 15 minutes, and washed with running water for 1minute. Thereafter, the hair was immersed into the second solution at30° C. for 15 minutes, washed with water, and shampooed. As the result,the white hair was imparted with a uniform wave from the root to thetip, and dyed in yellow color.

EXAMPLE 2

A Second Solution Composition of a Permanent Waving CompositionUtilizing Potassium Bromate

A second solution composition of the following formulation was preparedaccording to the conventional method.

Ingredient % 4-dimethylaminophenylazo-2N-methyl-5N-methylimidazolium 0.2chloride Potassium bromate 10.2 Lauryldimethyl acetate betaine 1.0Cetyltrimethylammonium chloride 0.6 Sodium benzoate 0.3 Salicylic acid0.05 Trisodium phosphate 0.27 Phosphoric acid, purified water Balance (ApH was adjusted to 6.5 with phosphoric acid)

The formulation of a first solution used was as follows.

Ingredient % L-cysteine hydrochloride 7.0 Cetanol 0.5 Oleyl alcohol 0.5Polyoxyethylene cetyl ether (10 E.O.) 1.0 Polyoxyethylene cetyl ether(15 E.O.) 1.0 Disodium editate 0.1 Monoethanolamine, purified waterBalance (A pH was adjusted to 9.0 with monoethanolamine)

The permanent waving and dyeing treatment of the hair were performedusing the first and second solution as described above according to thesame manner as that described in Example 1. As the result, the whitehair was imparted with a uniform wave from the root, and dyed in redcolor.

EXAMPLE 3

A Second Solution Composition of a Permanent Waving CompositionUtilizing an Enzyme

A second solution composition of the following formulation was preparedaccording to the conventional method. Uncase was added just before thetreatment with the second solution.

Ingredient % 4-aminophenylazo-2N-methyl-5N-methylimidazolium chloride0.2 Uricase (20 units/mg) 1.0 Uric acid 1.0 Glycerol 3.0 Purified WaterBalance

The formulation of a first solution used was as follows.

Ingredient % Ammonium thioglycolate solution 13.0 (50% as thioglycolicacid) Polyoxyethylene cetyl ether (10 E.O.) 1.0 Polyoxyethylene cetylether (20 E.O.) 1.0 Sodium laurylsulfate 0.5 Hydrolyzed collagensolution 0.4 Disodium editate 0.1 Aqueous ammonia, purified waterBalance (A pH was adjusted to 9.0 with aqueous ammonia)

The permanent waving and dyeing treatment of the hair were performedaccording to the same manner as that described in Example 1. As theresult, the white hair was imparted with a uniform wave from the root tothe tip, and dyed in orange color.

EXAMPLE 4

A Second Solution Composition of a Permanent Waving CompositionUtilizing Sodium Bromate

A two-packages composition consisting of an oxidative fixing solutionand an dye solution of the following formulation was prepared accordingto the conventional method.

Oxidative Fixing Solution

Ingredient % Sodium bromate 17.0 Lauryldimethyl acetate betaine 1.5Cetyltrimethylammonium chloride 1.0 Sodium benzoate 0.6 Salicylic acid0.1 Trisodium phosphate 0.54 Phosphoric acid, purified water Balance (ApH was adjusted to 6.5 with phosphoric acid)Dye solution

Ingredient % 4-(4-aminophenylamino)phenylazo-2N-methyl-5N- 0.4methylimidazolium chloride Monoethanolamine, purified water Balance (ApH was adjusted to 8.0 with monoethanolamin)

The same first solution as that described in Example 3 was used.

The permanent waving and dyeing treatment of the hair were performedaccording to the same manner as that described in Example 1, except thatan oxidative fixing solution and a dye solution were mixed in a ratio of1:1 upon application. As the result, the white hair was imparted with auniform wave from the root, and dyed in purple color.

EXAMPLE 5

A Second Solution Composition of a Permanent Waving CompositionUtilizing Sodium Bromate

A two-packages composition consisting of an oxidative fixing solutionand a dye solution of the following formulation was prepared accordingto the conventional method.

Oxidative Fixing Solution

Ingredient % Sodium bromate 8.5 Lauryldimethyl acetate betaine 1.0Cetyltrimethylammonium chloride 0.6 Sodium benzoate 0.3 Salicylic acid0.05 Trisodium phophate 0.27 Phosphoric acid, purified water Balance (ApH was adjusted to 6.5 with phosphoric acid)Dye Powder

Ingredient % (1-methyl-1-paramethoxyphenyl)-2-(1-methine-4N- 0.02methylpyridinium) hydrazine chloride (to the oxidative fixing solution)3-amino-7-(dimethylamino)-2-methoxyphenoxazine-5-ium 0.02 chloride (tothe oxidative fixing solution)

The same first solution as that described in Example 3 was used.

The permanent waving and dyeing treatment of the hair were conductedaccording to the same manner as that described in Example 1, except thatan oxidative fixing solution and dye powder were mixed in a ratio of10:1 upon co application. As the result, the white hair was impartedwith a uniform wave from the root, and dyed in green color.

EXAMPLE 6

Method for Dyeing Hair which has Been Permanently Waved

A dye solution of the following formulation was prepared.

Ingredient % (1-methyl-1-paramethoxyphenyl)-2-(1-methine-4N- 0.02methylpyridinium) hydrazine chloride hydroxyethyl cellulose 2.5Triethanolamine, purified water Balance (A pH was adjusted to 8.0 withtriethanolamine)

The same oxidative fixing solution as that described in Example 5 andthe same first solution as that described in Example 3 were used.

The permanent waving of hair was performed using a first solution and anoxidative fixing solution according to the same manner as that describedin Example 1. Thereafter, the dye solution was applied to the whitehair, and the white hair was allowed to stand at 30° C. for 30 minutes,washed with water, shampooed and dried. As the result, the white hairwas imparted with a uniform wave from the root to the tip, and dyed inyellow color.

INDUSTRIAL APPLICABILITY

According to the present invention, by incorporating or combiningcertain cationic dyes into or with a conventional second solutioncomposition of a permanent waving composition, there is provided asecond solution composition of a permanent waving composition which isexcellent in stability, dyeability and fastness. In addition, accordingto the present invention, by dyeing with the above composition, hairwhich has been permanently waved can be dyed with high dyeability andfastness, without deteriorating the effect of permanent waving.

1. A two-package kit for permanently waving hair comprising: (a) acationic dye solution comprising at least one cationic dye, wherein thecationic dye is present in an amount effective to color hair and has aquaternary nitrogen atom that is optionally delocalizable and an —X═N—bond, wherein X is a nitrogen atom or an —CH— group; (b) an oxidativefixing solution comprising at least one oxidative fixing agent forpermanently waving the hair; and (c) a reducing composition comprisingat least one reducing agent in a sufficient amount for waving hair. 2.The kit of claim 1, wherein the cationic dye is represented by formulaI:[A—Z═N—B]⁺X⁻  (II wherein Z is a nitrogen atom or a CH group; A and Bare independently of one another, a benzene ring or aromatic heterocyclegroup that is substituted or unsubstituted; and X⁻ is an anion.
 3. Thekit of claim 1, wherein the cationic dye comprises4-aminophenylazo-2-hydroxy-7-trimethylammoniumnaphthalene chloride,2-methoxyphenylazo-2-hydroxy-7-trimethylammoniumnaphthalene chloride,4-amino-3-nitrophenylazo-2-hydroxy-7-trimethylammoniumnaphthalenechloride,3-trimethylammoniumphenylazo-4N-phenyl-2-methyl-5-hydroxypyrazolechloride, (1-methyl-1-phenyl)-2-(1-methine-4N-methylpyridinium)hydrazine chloride,(1-methyl-1-paramethoxyphenyl)-2-(1-methine-4N-methylpyridinium)hydrazine chloride,(1-methyl-1-paramethoxyphenyl)-2-(1-methine-4N-methylpyridinium)hydrazine methylsulfate,4-dimethylaminophenylazo-2N-methyl-5N-methylimidazolium chloride,4-dimethylaminophenylazo-2N-methyl-3N-methylpyrazolium chloride,4-methylaminophenylazo-2N-methyl-5N-methylimidazolium chloride,4-aminophenylazo-2N-methyl-5N-methylimidazolium chloride,4-dimethylaminophenylazo-4N-methylpyridinium chloride,4-dimethylaminophenylazo-4N-oxidopyridinium chloride,4-(4-aminophenylamino) phenylazo-2N-methyl-5N-methylimidazolium, or3-amino-7-(dimethylamino)-2-methoxyphenoxazine-5-ium chloride, orcombinations thereof.
 4. A method of permanently waving hair comprising(a) applying a reducing solution to hair wherein the reducing solutioncomprises at least one reducing agent in a sufficient amount for wavinghair; (b) applying at least one oxidative fixing solution to the hairwherein the oxidative fixing solution comprises at least one oxidativefixing agent for permanently waving the hair; and (c) applying to thehair at least one cationic dye in an amount effective to color the hairand having a quaternary nitrogen atom that is optionally delocalizableand an —X═N— bond, wherein X is a nitrogen atom or a —CH— group, andwherein the catatonic dye is applied to the hair as a component of theoxidative fixing solution.
 5. The method of claim 4, wherein thecationic dye is represented by formula I:[A—Z═N—B] ⁺X⁻  (I) wherein Z is a nitrogen atom or a CH group; A and Bare independently of one another, a benzene ring or aromatic heterocyclegroup that is substituted or unsubstituted; and X⁻ is an anion.
 6. Themethod of claim 5, wherein A or B or both have one or more substituentsselected from halogen atoms, NR₁R₃ groups, or OR₁ groups, wherein R₁ andR₂ are independently selected from hydrogen, a C₁ to C₆ alkyl group, aC₁ to C₄ hydroxyalkyl group, or a phenyl group.
 7. The method of claim6, wherein the cationic dye comprises4-aminophenylazo-2-hydroxy-7-trimethylammoniumnaphthalene chloride,2-methoxyphenylazo-2-hydroxy-7-trimethylammoniumnaphthalene chloride,4-amino-3-nitrophenylazo-2-hydroxy-7-trimethylammoniumnaphthalenechloride,3-trimethylammoniumphenylazo-4N-phenyl-2-methyl-5-hydroxypyrazolechloride, (1-methyl-1-phenyl)-2-(1-methine-4N-methylpyridinium)hydrazine chloride,(1-methyl-1-paramethoxyphenyl)-2-(1-methine-4N-methylpyridinium)hydrazine chloride,(1-methyl-1-paramethoxyphenyl)-2-(1-methine-4N-methylpyridinium)hydrazine methylsulfate,4-dimethylaminophenylazo-2N-methyl-5N-methylimidazolium chloride,4-dimethylaminophenylazo-2N-methyl-3N-methylpyrazolium chloride,4-methylaminophenylazo-2N-methyl-5N-methylimidazolium chloride,4-aminophenylazo-2N-methyl-5N-methylimidazolium chloride,4-dimethylaminophenylazo-4N-methylpyridinium chloride,4-dimethylaminophenylazo-4N-oxidopyridinium chloride,4-(4-aminophenylamino)phenylazo-2N-methyl-5N-methylimidazolium, or3-amino-7-(dimethylamino)-2-methoxyphenoxazine-5-ium chloride, orcombinations thereof.
 8. The method of claim 4, wherein the catatonicdye is present in the oxidative fixing solution in an amount of from0.001 weight percent to 3 weight percent, based on the total weight ofthe solution.
 9. The method of claim 4, wherein the solution containingthe cationic dye has a pH of 5 or greater.
 10. The method of claim 9,wherein the solution containing the cationic dye comprises 60 weightpercent or greater water.